title: Fe-catalyzed one-pot oxidative cleavage of unsaturated fatty acids into aldehydes with hydrogen peroxide and sodium periodate.
abstract: A one-pot method has been developed for the oxidative cleavage of internal alkenes into aldehydes by using 0.5 mol% of the nonheme iron complex [Fe(OTf)2(mix-bpbp)] (bpbp=N,N'-bis(2-picolyl)-2,2'-bipyrrolidine) as catalyst and 1.5 equivalents of hydrogen peroxide and 1 equivalent of sodium periodate as oxidants. A mixture of diastereomers of the chiral bpbp ligand can be used, thereby omitting the need for resolution of its optically active components. The cleavage reaction can be performed in one pot within 20 h and under ambient conditions. Addition of water after the epoxidation, acidification and subsequent pH neutralization are crucial to perform the epoxidation, hydrolysis, and subsequent diol cleavage in one pot. High aldehyde yields can be obtained for the cleavage of internal aliphatic double bonds with cis and trans configuration (86-98%) and unsaturated fatty acids and esters (69-96%). Good aldehyde yields are obtained in reactions of trisubstituted and terminal alkenes (62-63%). The products can be easily isolated by a simple extraction step with an organic solvent. The presented protocol involves a lower catalyst loading than conventional methods based on Ru or Os. Also, hydrogen peroxide can be used as the oxidant in this case, which is often disproportionated by second- and third-row metals. By using only mild oxidants, overoxidation of the aldehyde to the carboxylic acid is prevented.
authors.affiliation: Organic Chemistry and Catalysis, Department of Chemistry, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands), Fax: (+31) 30-2523615.
authors.forename: Peter
authors.initials: P
authors.lastname: Spannring
authors.forename: Vital
authors.initials: V
authors.lastname: Yazerski
authors.forename: Pieter C A
authors.initials: PC
authors.lastname: Bruijnincx
authors.forename: Bert M
authors.initials: BM
authors.lastname: Weckhuysen
authors.forename: Robertus J M
authors.initials: RJ
authors.lastname: Klein Gebbink
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D005231:Fatty Acids, Unsaturated / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010504:Periodic Acid / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D005231:Fatty Acids, Unsaturated; D010504:Periodic Acid; C009288:metaperiodate; D006861:Hydrogen Peroxide; D007501:Iron
keywords: aldehydes; alkenes; cleavage reactions; fatty acids; hydrogen peroxide; iron